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A large petrochemical complex, dubbed Petro–complex, situated in a rather rural region of Taiwan, was used as a test bed to detect emissions from the Petro–complex to its surroundings. Hourly observations of speciated non–methane hydrocarbons (NMHCs) by the photochemical assessment monitoring stations (PAMSs), as well as the total amounts of NMHCs, SO₂, and NO_x provided by the air quality stations (AQSs), were utilized to find useful petro–emission indication methods. The analytical aspect of NMHCs either as a speciated form or as total amounts was demonstrated through field comparison to illustrate data quality. Using ethyne to offset traffic influence, the ratios of ethene to ethyne (acetylene) (E/A) and propene to ethyne (P/A) were proven to be effective indicators of petro–emissions owing to pronounced emissions of ethene and propene, revealed as tall spikes in PAMS measurements. SO₂ and NO_x were also explored as petro–emission indicators mainly for stack sources. By coordinating with three–dimensional modeling, SO₂ from petro–emissions could be distinguished from other prominent sources, such as coal–fired power plants. An attempt was also made to use SO₂ and NO_x as indicators of broader petro–emissions with stringent criteria to minimize traffic interference and increase specificity. Similar findings were observed with the three indicators, that is, volatile organic compounds (VOCs) ratios, SO₂ and NO_x, to identify the southwest area of the Petro–region as the most affected area, as represented by Taisi station (F2). The percent affected time of a year at F2 was 10%–14%, owing to the dominant wind field of northeast monsoonal (NEM) in the region, as compared with other sites in the east and north of 1–5%. Using VOC ratios as petro–emission indicators is more effective than using other gases, owing to the compositional advantage to minimize traffic interference. Full article